Composition and method for the treatment of soil



United States Patent 3,319,377 COMPOSITION AND METHOD FOR THE TREATMENTOF SOIL John C. Tapas, Glenview, and John M. Menke, Morton Grove, Ill.,assignors to Velsicol Chemical Corporation, Chicago, 111., a corporationof Illinois No Drawing. Filed Aug. 27, 1964, Ser. No. 392,587

21 Claims. (Cl. 47-9) This application is a continuation-in-part of ourcopending application, S.N. 266,171, filed Mar. 19, 1963, now abandoned,which in turn is a continuation-in-part of our application, S.N.188,233, filed Apr. 17, 1962, copending therewith and now abandoned.

This invention relates to a composition and method for the treatment ofsoil to reduce soil erosion. More particularly this invention relates tothe reduction of soil erosion which comprises applying to the surface ofthe soil a liquid composition of a thermoplastic petroleumderivecl,hydrocarbon resin; a linear vinyl polymer; and a diluent therefor.

In the reduction and prevention of soil erosion it is usually desirablethat plants and grasses grow and become firmly established in areassubject to erosion, not only to prevent erosion, but also to improvesoil fertility and soil structure, and for the aesthetic value of thegrass and plants. While under ideal conditions seeds of plants andgrasses germinate and grow naturally in the absence of artificialprotection, i.e., soil treatment, the conditions which cause erosion,such as high winds and excessive rainfall, often cause seeds and soil tobe washed or blown away and young plants to be uprooted. These effectsare particularly noticeable on sloping terrains, such as on hills,mountains, river embankments, road shoulders and enrbankments, and thelike.

Various attempts have been made to protect the soil rom erosion. Some ofthese attempts comprised covering the soil with permanent imperviouscontinuous coatings, such as cement, asphalt and allied substances, andthe like. While these coatings prevent wind and water from reaching thesoil, they also prevent the germination of plant and grass seeds andtheir growth through the coating. Other attempts to control erosion,such as coating the soil with rubber latex, resinous materials, straw,paper, .pulp, mulches, and the like have also generally failed, eitherdue to the dissipation of the coatings or coverings before the seedscould germinate and mature, as in the case of most rubber latex andresinous coatings; or because they were unsightly, as in the case of theother stated materials. Further attempts in the case of rubber latex andresinous materials, to slow the dissipation of the coatings byincreasing the thickness of the coating, merely served to preventgermination and/or retard or prevent the growth of grasses and plantsthrough the coating. Often the growing plants could not penetrate thecoatings.

Thus, despite the attempts heretofore made to control soil erosion,there is still a need for a method of controlling and preventing soilerosion, which also protects seeds from being Washed or blown awayduring germination and permits young plants and grasses to growunhindered through the soil surface.

Therefore, it is one object of the present invention to provide a methodfor the effective control of erosion of soil.

It is another object of the present invention to provide a methorl forthe protection of soil and of seeds planted therein from erosion causedby wind and rain.

Still another object of this invention is to provide a method for thecontrol of erosion of soil and to assist the germination of grass andplant seeds.

Another object is to provide a method for the control of erosion of soilcomprising chemical pest control agents and to protect the growth ofdesirable plants from'injury by insects, fungi, Weeds, and the like.

Another object is to provide a novel composition useful in the foregoingmethods.

These and other objects of the present invention will be apparent fromthe ensuing description.

The foregoing objects can be accomplished by the method of the presentinvention which comprises applying to the soil surface a liquidcomposition comprising a thermoplastic, petroleum-derived, hydrocarbonresin; a linear vinyl polymer; and a diluent therefor. It is preferredthat the liquid composition described above be a water dispersible orwater dilutible composition, wherein the resin and polymer are presentas aqueous emulsions, and the diluent is water.

It is unexpected and highly novel that the use of the liquid compositiondisclosed herein should accomplish the objects set forth above, when useof aqueous emulsions of either the thermoplastic, petroleum-derived,hydrocarbon resin or the linear vinyl polymer alone do not accomplishthese objects. Hence, it is the use of the combination of theingredients in the liquid composition disclosed herein which affords thedesirable results of this invention, which cannot be obtained orpredicted from the use of the component ingredients themselves. Likematerials heretofore utilized in attempts to control soil erosion, theapplication of the individual ingredients separately either does noteifeetively prevent soil erosion due to rapid dissipation of the coatingor prevents erosion only when applied in a concentration which alsoprevents seed germination and the passage of air and water through thecoating.

In carrying out the method of the present invention, it is preferred toutilize a thermoplastic petroleum derived hydrocarbon resin having asoftening point of from about to about 200 F. (ball and ring method) asthe resin ingredient in the above-described liquid composition. It ismore preferred to use a thermoplastic petroleum-derived hydrocarbonresin having a softening point of from about 50 to about 200 F., a mixedaniline point of from 20 to about 80 C., and an iodine number of fromabout to about 300, as the resin ingredient,

The resin utilized in the process of the present invention can beproduced by thermal or catalytic polymerization of unsaturated petroleumhydrocarbon fractions by methods and procedures common to the art.

It is even more preferred to use as the resin ingredient in the liquidcomposition utilized in the method of the present invention, athermoplastic petroleum-derived hydrocarbon resin having a softeningpoint of from about 50 to about 200 F., a mixed aniline point of fromabout 20 to about C., an iodine number of from about 70 to about 300, asaponification number of from 0 to about 2, a flash point (ClevelandOpen Cup) above 350 F., an A.P.I. gravity at 60 F. of from 0 to about 20degrees, 21 Gardner color (50% toluene) of from about 1 to about 12, anda molecular weight of from about 300 to about 1400 as measured bycryosco-pic means.

An especially preferred resin ingredient of the composition used in themethod of the present invention, hereinafter designated Resin A, is athermoplastic petroleumderived, substantially completely polymerized,aromatic, hydrocarbon resin having a softening point of from about toabout 200 F., a mixed aniline point of from about 20 to about 60 C., aniodine number of from about 70 to about 220, a saponification number offrom 0 to about 2, a flash point (Cleveland Open Cup) above 425 F., anA.P.I. gravity at 60 F., of from O to about 10 degrees, a Gardner color50% toluene) of from about 1 to about 12, and a molecular weight of fromabout 600 to about 1400 as measured by cryoscopic means.

A second especially preferred resin ingredient, hereinafter designatedResin B, is a thermoplastic, petroleumderived hydrocarbon resin composedsubstantially of tetramers, pentamers, hexamers, heptamers, octamers,and higher polymers of conjugated aliphatic and cyclic dienes havingless than 7 carbon atoms per diene monomer, and having a softening pointof from about 50 to about 100 F., a mixed aniline point of from about 40to about 80 C., an iodine number of from about 200 to about 300, asaponification number of from to about 2, a flash point (Cleveland OpenCup) above 350 F., an A.P.I. gravity at 60 F., of from 0 to about 20degrees, a Gardner color (50% toluene) of from about 1 to about 12, anda molecular weight of from about 300 to about 600 as measured bycryoscopic means. Examples of conjugated aliphatic dienes suitable foruse in preparing Resin B are: isoprene, cis-piperylene,trans-piperlylene, 1,3-hexadiene, and 2,4- hexadiene; while examples ofsuitable conjugated cyclic dienes are: cyclopentadiene,methylcyclopentadiene, and 1,3-cyclohexadiene.

A particularly preferred Resin B is the tetramer and higher polymerfraction which has an A.P.I. gravity of from about 5 to about degrees,and which is produced from a liquid petroleum hydrocarbon streamcomposed substantially of dimers, trimers, codimers, and higher polymersof conjugated aliphatic and cyclic dienes having less than 6 carbonatoms per diene monomer molecule. The said liquid petroleum hydrocarbonstream can be fractionally distilled, preferably in vacuo, to recoverthe tetramer and higher polymer fraction (Resin B) as the residue.

The linear vinyl polymer ingredient of the liquid composition utilizedin the method of this invention is selected from the group consisting ofhomopolymers and copolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, their copolymerswith vinyl esters of long chain fatty acids, their copolymers withdi(alkyl esters) of a, fi-ethylenically unsaturated dicarboxylic acids,preferably wherein the alkyl ester group contains from 4 to 18 carbonatoms, and mixtures thereof. Exemplary of the vinyl esters of long chainfatty acids suitable for copolymerization with the monomers describedabove to form linear vinyl polymer ingredients are: vinyl myristate,vinyl palmitate, vinyl stearate, vinyl laurate, and the like. Exemplaryof the suitable di(alkyl esters) of a, ,B-ethylenically unsaturateddicarboxylic acids which can be copolymerized with the vinyl monomersdescribed above to form the linear vinyl polymer ingredient are: dibutylmaleate, dioctyl mateate, dibutyl fumarate, and the like. Thesepolymers, their plasticized products and inherently plasticizedcopolymers are commer cially available or can be readily prepared bymethods common to the art.

The resin and polymer ingredients are combined with a liquid diluent toform the liquid composition utilized in the method of the presentinvention. The diluent must be inert, that is, unreactive with the resinand polymer ingredients and harmless to growing plants and grasses.Organic inert solvents can be used if desired, although the preferreddiluent is water. Since the resin and polymer ingredients heretoforedescribed are insoluble, they must be emulsified to form an emulsionwith the water.

Emulsions of the linear vinyl polymer ingredient are commerciallyavailable or can be prepared by methods common to the art, such as byemulsion polymerization with emulsifiers, such as sodium stearate andthe like. It is preferred to utilize a polyvinyl acetate homopolymer ora vinyl acetate-vinyl ester of a long chain fatty acid copolymeremulsion as the polymer ingredient. An example of a suitable vinylacetate copolymer emulsion is the emulsion of a vinyl acetate-vinylstearate copolymer, which is commercially available, or alternativelycan be prepared by methods common to the art, such as by emulsionpolymerization.

It is even more preferred to utilize as the linear vinyl polymeringredient an emulsion of a copolymer of vinyl acetate and a di(a-lkylester) of an a, fi-ethylenically unsaturated dicarboxylic acid. Atypical emulsion as described above is an aqueous emulsion containing55% solids consisting primarily of a copolymer of vinyl acetate anddibutyl maleate. Such an emulsion is commercially available as Flexbond800 marketed by the Air Reduction Company, New York, New York, USA.

The resin ingredient is also preferably utilized in the form of anemulsion. A typical resin-in-water emulsion composition useful in themethod of this invention can be readily prepared by heating the resinuntil almost molten, adding emulsifiers, and, if desired, Wettingagents, and mixing with water until an emulsion is formed. At first awater-in-resin emulsion is formed, which can be slowly mixed through aninversion period to yield a concentrated resin-in-water emulsion. Thisemulsion can be further diluted to any desired concentration. Thetemperature at which the emulsion is prepared is dependent upon thesoftening point of the resin and will usually correspond thereto.

The emulsifiers and wetting agents useful with the resin describedherein to prepare the compositions utilized in the method of the presentinvention are surface-active materials of the anionic or nonionic types.Preferably a combination of the two types is used to obtain rapidemulsions of excellent stability. Typical examples of such surfaceactivematerials are sodium stearate, morpholine oleate, sodium lauryl sulfate,sodium Z-ethylhexyl sulfate, sodium Z-ethylhexanol-l-sulfate, sodium7-ethyl-2-methylundecanol-4-sulfate, sodium naphthalenesulfonate, sodiumalkylnaphthalenesulfonate, sodium oleic acid sulfonate, sodium castoroil sulfonate, glycerol monostearate containing a soap (or a sodiumfatty alcohol sulfate), polyoxyethylene fatty alcohol ethers, polyglycolfatty acid esters, polyoxyethylene modified fatty acid esters,polyoxyethylenepolyol fatty acid esters, polyoxypropylene fatty alcoholethers, polypropylene glycol fatty acid esters, polyoxypropylenemodified fatty acid esters, polyoxypropylenepolyol fatty acid esters,polyol fatty acid monoe-sters, diand higher polyhydric alcohol fattyacid esters, cholesterol and other fatty acid esters, lanolin, oxidizedfatty oils, alkylated aryl polyether alcohols such as the condensationproduct of diamylphenol with ethylene oxide, and the like. Mixtures ofsuch materials can also be used to combine or modify properties.

Emulsions of the resin ingredient and the polymer ingredient can readilybe combined for example, by stirring together in a suitable vessel, suchas a mixing tank, to form a concentrated mixture. This liquidconcentrate can be diluted with water to any desirable concentration toform the liquid composition utilized in the process of this invention.It is preferred to utilize from about 20% to about 85%, by weight of themixture, of the resin-in-water emulsion with from about 15% to about byweight of the mixture, of the polymer-in-water emulsion in preparing themixture. Emulsions of the resin and polymer ingredients containing aminimum amount of water are preferred for economy, although more diluteemulsions can be utilized with equal success. For example, emulsion-scontaining from about 40% to about 60% solids by weight have been foundto be convenient in forming the mixture described above.

The preparation of the liquid compositions utilized by the method of thepresent invention will be more clearly understood from the followingexamples:

EXAMPLE I Preparation of an emulsion of Resin A Resin A (578.5 gm.),which was a thermoplastic, petroleum derived, substantially completelypolymerized, aromatic, hydrocarbon resin having a softening point of140150 F., a mixed aniline point of 3236 C., an iodine number of145-155, a saponification number of 2, a flash point (Cleveland OpenCup) above 425 F., an A.P.I. gravity at 60 F. of 04.5 degrees, a Gardnercolor (50% toluene) of -10, and a molecular weight of about 1000 asmeasured by cryoscopic means: was heated at about 190 F. until the resinwas alrnost molten. A nonionic surfactant of the octyl phenoxypolyoxyethylene ethanol type (5.8 gm.), soya fatty acid (52.0 gm.), and2-amino-2-methylpropanol (15.8 gm.) were mixed into the almost moltenresin until a uniform mixture was formed. Water (695 gm.) was slowlyadded at the temperature of the mixture with agitation by means of apaddle stirrer driven at a maximum speed of 875 revolutions per minute.vAt first a water-in-resin emulsion was formed, but on continuedstirring with continuous addition of water the emulsion inverted to aresin-in-water emulsion 'as indicated by the change from a doughyconsistency to a uniform milky consistency. After all of the water hadbeen added the emulsion concentrate thus formed had a viscosity of 54Krebs units, a solids content of 51.0 by weight, a pH of 8.8, and adensity of 8.45 pound-s per gallon.

EXAMPLE 2 Preparation of Resin B A hydrocarbon-bottoms stream composedsubstantially of dimers, trimers, codimers, cotrimers and higherpolymers of conjugated aliphatic and cyclic dienes, and having thefollowing physical properties: A.P.I. gravity at 60 F., 26 degrees;Gardner color, 3; viscosity (S.S.U. at 100 F.), 43 sec.; flash point(Cleveland Open Cup), 135- 138 F.; iodine number, 326; and anilinepoint, 34.2 C.; was heated at 590-595 F. for 4 hours. Dimers, trimers,codimers, and cotrimers were distilled off by heating to a pottemperature of 575 F. at 1 0 mm. mercury pressure, to yield Resin B asthe residue, having a softening point of 74 'F., a mixed aniline pointof 69.4" C., an iodine number of 276, a saponifica-tion number of 0 2, aflash point (Cleveland Open Cup) of 375 F., a Gardner color (50%toluene) of 6-7, and a molecular weight of 200- 600 as determined bycryoscopic means.

EXAMPLE 3 Preparation of an emulsion of Resin B Resin B (578.5 gm.)prepared as in Example 2, was heated to 120 -140," -F. A nonionicsurfactant, nonyl phenoxy polyoxyethylene ethanol (43.1 gm.), and thesodium salt of an alkyl aryl polyether sulfonate (14.7 gm.) were mixed.into the almost molten resin until a uniform mixture was obtained.Water (500 gm.) was slowly added at 120140 F. with agitation provided bya paddle stirrer driven at a maximum speed of 875 revolutions perminute. A water-in-resin emulsion was first formed which inverted t0resin-in-water emulsion as indicated by the changefrom doughy to milkyconsistency. After all of the water had been added the emulsion thusformed had a viscosity of 47 Kreb units, a solids content of 53.6% byweight, and a pH of 7.6.

EXAMPLE 4 Preparation of a concentrated mixture of emulsions Emulsionproduct of Example 3 (200 gms.) and 200 grams of a commercially obtainedvinyl acetate-dibutyl maleate copolymer emulsion Flexbond 800, marketedby Air Reduction Company, New York, N.Y., having a viscosity of 550850centipoises, a solids content of 51- 53%, a pH of 5.0-6.0, a particlesize of about 0.7 microns, and a density of about 9.pounds per gallon;were placed into a one pint metal can and stirred with a spatula untiluniformly blended. Thus 400 grams of a concentrated mixture of theemulsions of Resin B and vinyl acetate copoiymer were obtained.

In the manner described in Example 4, other concentrated mixtures ofemulsions can be prepared. In illustration of the preparation of theseother mixtures, the following examples are presented wherein thematerials specified can be blended according to the procedure of Example4 to yield the corresponding mixture:

Emulsion of Emulsion of Polymer Emulsion Ex. Resin A, Resin B, No.Product of Product of Example 1, Example 3, Type Wt., wt., grns. wt.,gins. gins.

5 200 Vinyl acetate-dibutyl 200 maleate copolymcr (Flexbond 800"). dodo.. 300 do 100 do 300 Polyvinyl chlorid 200 Polyvinyl alcohol. 200Ethyl acrylate- 100 methyl methacrylate copolymer. 13 200 Vinylchloride-vinyl 220 acetate copolyrner.

The concentrated mixtures heretofore described can also be readilypigmented to impart color into the liquid composition utilized in thisinvention. Pigments can be added, for example, by preparing a dispersionof the pigments in water and blending the dispersion with the resin andpolymer emulsions according to the method of Example 4. The applicationof the pigmented liquid compositions according to the method of thepresent invention, provides a colored coating on the surface of the soilwhich has a desirable aesthetic value and also serves as an indicator ofthe presence of the coating.

Concentrated mixtures of the emulsions, as heretofore described, arepreferably diluted with water to form the liquid compositions used inthe method of this invention. While relatively concentrated compositionscan be used to obtain thick coatings of the resin and polymer mixture onthe soil, it is preferred to utilize aqueous composi tions comprisingfrom about 5% to about 20% by volume of concentrated mixture ofemulsions to obtain the desired soil penetration and binding effects.

The liquid compositions utilized in the method of the present inventioncan be sprayed onto the surface of the soil by methods and procedurescommon to the art, such as by hand sprayers, commercial field sprayers,and the like. The compositions penetrate the soil to a depth dependingon the porosity of the soil, the dilution of the composition, and therate of application. It is preferred to apply the liquid composition ina soil stabilizing amount, i.e., in an amount adequate to bind the soilparticles in the upper layers of the soil and form a thin film ofmaterial on the surface. It has been found adequate to apply the liquidcomposition at a rate of at least about 700 gallons per acre of soilsurface, and preferably between about 800 and 2,000 gallons per acre toobtain maximum penetration and binding properties.

The method of this invention provides the binding of the top layers ofsoil and a continuous coating on the surface of the soil, which preventthe erosion of top soil by wind and water. The binding of the soil andcoating are usually effective for a period of approximately 6 weekswhich is generally sufiicient for the germination and established growthof most grasses and plant seeds. The treatment also assists thegermination of plant and grass seeds, and offers little or no resistanceto the passage of air and water through the coating and to grass orseedlings pushing through the treated soil and coating. The treated soilfurther protects the root structure of young grass and plant seedlingsfrom being damaged or uprooted by wind or water.

The liquid compositions utilized in the method of this invention canalso comprise such additional substances as pesticides, such asherbicides, insecticides, miticides,

aphicides and fungicides; fertilizers, activators, stimulants, and thelike. Throughout this specification the term pesticide will be usedsynonymously with the term pesticidal chemical compound. The use of oneor more of these additional substances will provide the desirablebenefits of the method of this invention plus the benefits of the addedsubstances.

For example, the incorporation of herbicidal chemical compounds into theliquid compositions utilized in the method of this invention will resultnot only in the control of soil erosion but in the control ofundesirable weeds in the soil as Well. A further advantage of suchcompositions is that their use will permit control of the depth towhichthe herbicide permeates into the soil. As a result, normallynonselective herbicides or soil sterilants, which kill all the plantgrowth in the area where they are employed, can be made comparativelyselective in their action. That is, the penetration into the soil of acomposition of this invention comprising a nonselective herbicide can becontrolled by proper dilution and rate of application as previouslydiscussed so that minimal penetration is obtained. The herbicide willtherefore have only localized activity near the surface of the soil,where it can attack short-rooted weeds such as the grassy weeds. At thesame time, its penetration into the soil will not be sufficient toaffect the deep roots of many commercial crops.

A wide variety of herbicidal chemical compounds known to the art can beused in the method and compositions of this invention. These can includechlorophenoxy herbicides such as 2,4-dichlorophenoxyacetic acid,2,4,S-trichlorophenoxyacetic acid, Z-methyl-4-chlorophenoxyacetic acid,3,4-dichlorophenoxyacetic acid, parachlorophenoxyacetic acid,4-(2,4-dichl-orophenoxy)butyric acid,

4- 2-methyl-4-chlorophenoxy butyric acid, 4- 2,4,5 -trichlorophenoxy)b-utyric acid, and 2- 2,4,5 -trichlorophenoxy propionic acid;

carbamate herbicides such as isopropyl N-phenylcarbam ate, i isopropylN-(3-chlorophenyl)carbamate, and 4-chloro-2-butynyl N- 3-chlorophcnylcarbamate;

substituted urea herbicides such as dichloral urea,

3-phenyl-l l -dimethy'lurea,

3- pana-chlorophenyl) 1 l-climethylurea,

3- 3 ,4-dichlorophenyl 1 l-dimethylurea, and l-n-butyl-S 3,4-dichlorophenyl 1 -methylurea;

symmetrical triazine herbicides such as 2-chloro-4,6-bis diethylamino-s-triazine, 2-chloro-4,6-bis ethylamino) -s-triaz ine,2-chlor0-4-ethylamino-6-isopropylamino-s-triazine,2-chloro-4ethylamino-6-diethylamino-s-triazine, 2-chloro-4-diethylamino-6-isopropylamino-s-triazine, 2-methoXy-4,6bis ethylaminos-triazine, 2-methoxy-4,6-bis (isopropylamino -s-triazine, and2-chloro-4,6-bis diisopropylamino -s-triazine;

chloroacetamide herbicides such as alpha-ch10 ro -N,N-dimethylacetamide,alpha-chloro-N,N-d-iethylacetamide,alpha-chlo-ro-N,N-di-n-propylacetamide,alpha-chloro-N,N-diallylacetamide, alpha-chloro-N-propylacetamide,alpha-chloro-N-isobutylacetamide, alpha-chloro-N-sec-butylacetamide,alpha-chloro-N-isoamylacetamide,

4- (chloroacetyl morpholine, and

1- (chloroacetyl piperidine;

8 chlorinated aliphatic acid herbicides such as trichloroacetic acid,2,2-dichloropropionic acid, 2,3-dichloroisobutyric acid,2,2-trichloropropionic acid, and 2,3,3-trichloroisob utyric acid;

thiooarbamic acid and dithioca-rbamic acid herbicides such 2-chloroallyldiethyldithiocarbamate, sodium N-methyldi thiocanbamate, ethylN,N-di-n-propylthiocarbamate, n-propyl di-n-propylthiolcarbamate, ethylethyl-n-butylthiolca-rbamate, and propyl ethyl-n-butyl thiolcarbamate;

chlorinated benzoic acids and phenylacetic acids such as2,3,6-trichlorobenzoic acid,

2,3,5 ,6-tetrachlorobenzoic acid,

2-methoxy-3 ,6-d-ichlorobenzoic acid,

2-methoxy-3 ,5 ,6-trichlorobenzoic acid, 2-methoxy-3,6-dichlorophenylacetic acid, 2-methoxy-3,5,6-trichlorophenylaceticacid,

2,3 ,6-trichlorophenylacetic acid, 3-methoXy-2,6-clioh-lorophenylaceticacid, 2-methoxy-S-chloro-6-methylphenylacetic acid, and2-metl1oxy-3-nitro-5-chlorobenzoic acid;

and such herbicides as aminotriazole,

maleic hydrazide,

disodium 3,6-endoxohexahydrophthalate, N-l-naphthylphthalamic acid,

N- l -naphthylphthalimide,

aorolein,

2,3-dichloroallyl diisopropylthiolcarbamate, biuret,

technical chlordane consisting preponderantly of the compoundl,2,4,5,6,7,8,8-octachloro-4,7-methano-3a,4,7,7a-tetrahydroindane (theremainder being related active compounds arising during themanufacturing process),

dimethyl 2,3 ,5 ,6-tetrachloro-terephthalate,

l,l-ethy-lene-2,2-dipyridilium dibromide,

2- 2,4,5 -trichlorophenoxy ethyl 2,2-dichloropropionate,

the betaand gamma-isomers of 4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7-methanoindene (M.P. 210- 21 1 under nitrogen),

tris 2,4-dichlorophenoxyethyl phosphite,

3 ,4-dichlozropropionanilide,

3 ,5 -dimethyltetrahydro- 1 ,3 ,5 ,ZH-thiadiazine-Z-thione,

N- 3 ,4-dichlorophenyl -2-methylpentanarnide,

N- 3 -chloro-4-methylphenyl) Z-methylpentanamide,

N- (3 ,4-dichlorophenyl methacrylamide, and

O-( 2,4-dichlorophenyl) O-methyl isopropylphosphoramidothioate.

Such herbicides can also be used in the method and compositions of thisinvention in the form of their salts, esters, amides, and otherderivatives whenever applicable to the particular parent compounds.

Similarly, the incorporation of insecticidal chemical compounds into theliquid compositions utilized in the method of this invention will resultnot only in the control of soil erosion but in the control ofundesirable insect pests in the soil as well. A Wide variety ofinsecticidal chemical compounds known to the art can be used in themethod and compositions of this invention. Typical examples of suchinsecticidal chemical compounds are halogenated compounds such as l, l l-trichloro-2,2-bis p-chlorophenyl) ethane, 1,1,1-trichloro-2,2-bis(p-methoxyphenyl) ethane, l, l-dichl-oro-2,2-bis(p-chloirophenyl ethane, hexachlorocyclohexane,

1,2,4,5,6,7,8,8-octachloro-4,7-methano-3 a,4,7,7a-tetrahydroind ane,

l,2,3,4,10,IO-hexachloro-1,4,4a,5,8,8a-hexahydro-1,4, 5,8-

dimethauonaphthalene,

1,2,3,4,10,l-hexachloro-6,7-epoxy-1,4,4a,5,6,7,8,8a-octahydro-1,4,5,8-dimethanonaphthalene,

1,4,5 ,6,7 ,8,8-heptachloro-3 a,4,7,7 a-tetrahydro-4,7-methanoindene,

1,2,3 ,4,10,10-hexachloro-6,7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-1,4,5,8-endo,endo-dimethanonaphthalene,

6,7, 8,9, l 0, 1 O-hexachlorol ,5,Sa,6,9,9a-hexahydro-6,9-

methano-2,4,3-benzodioxathiepin-3-oxide, and

4,4'-dichlorobenzila te organic phosphorus compounds such as tenraethylpy-rophosphate,

0,0-diethyl O-p-nitrophenyl thiophosphate,

O-ethyl O-p-nitrophenyl phenylthiophosphonate,

octamethylpyrophosphoramide,

0,0-diethyl O-(2-ethylmercapto)ethylphosphorothioate,

0,0-diethyl s- (ethylmercapto methylphosphorodithioate,

0,0-diethyl O- 4-methyl-7-coumarinyl) phosphorothioate,

0,0-diethyl O- 2-isopropyl-6-methyl-4-pyrimidinyl) phos' phorothioate,

0,0-dimethyl s-( 1,2-dicarbethoxyethyl phosphorodithioate,

0,0-dimethyl s- 4-oxobenz0t-riazino-3-methy1) phosphorodithioate,

0,0-dimethyl O- 3 -chloro-4-nitrophenyl) phosphorothioate,

0,0-dimethyl l-hydroxy-2,2,Z-triohloroethylphosphonate,

and

dimethyl 2,2-dichlorov-inyl phosphate;

organic nitrogen compounds such as 4,6-dinitro-o-cresol,2,4-dinitro-6-cyclohexylphenol, and azobenzene;

organic sulfur compounds such as phenothiazine,

phenoxathiin,

lauryl thiocyanate,

beta,beta'-dithiocyanodiethyl ether (bis (2-thiocyanoethyl ether) andisobornyl thiocyanoacetate;

as well as such substances, usually refenred to as fumigants, ashydrogen cyanide, carbon tetrachloride, ethylene dichloride, propylenedichloride, paradichloro'benzene, and the like.

The liquid compositions utilized in the method of this invention canalso comprise fungicidal chemical compounds, useful for the control ofsoil fungi and in some cases of soil nematodes as well. Typical examplesof such fungicidal chemical compounds are ferric dimethyldithiocarbamate, disodium ethylenebisdithiocarbamate, Zincethylenebisdithiocarbamate, tetramethylthiurarn disulfide, tetrachloro pbenzoquinone, 2,3 dichloro- 1,4-naphthoquinone,2-n-heptadecylglyoxalidine,N-(trichloromethylthio)-l,2,3,6-tetrahydrophthalimide,2-heptadecyl-Z-imidazoline, 2,4-dichloro-6-(o-chloroanilino) triazine,and the like.

Many of the pesticidal chemical compounds known in the pesticide art aresolids or are liquids insoluble in Water. Such pesticides can beincorporated into the compositions of this invention by first dissolvingthem in a suitable inert organic solvent as previously discussed andthen blending the solutions with the composition to be used forapplication to the soil. If desired, emulsifiers and wetting agents ofthe type shown herein to be useful for the resins in this invention canalso be used in the pesticide solutions to enhance their ability toblend homogeneously with the resin emulsions.

The rate at which the pesticides can be used in the method andcompositions of this invention will be deter mined largely by thespecific type of pesticide employed and by the species of pests to becontrolled. Generally, the instructions of the pesticides manufacturercan be followed, and the quantity of the pesticide can be adjusted sothat it is present in the composition in a pesticidally toxic amount.Many pesticides can be use-d at the rate of only one or two ounces peracre, while others will be used at rates of at least one pound or moreper acre. Such rates of application can be obtained by adjusting theamount of pesticide added to the aqueous compositions before they areapplied to the soil, and it is particularly convenient for this purposeto add the pesticide in the form of a solution in an inert organicsolvent with an emulsifier or wetting agent or in the form of an aqueousemulsion prepared by extending the solution with water. In a preferredembodiment of this invention, the aqueous compositions for the treatmentof soil will comprise from about 5% to about 20% by volume of a mixtureof hydrocarbon resin-in-water emulsion and linear polymer-in-wateremulsion and from about 50% to about 95% by volume of pesticidalchemical compound-in-water emulsion.

The eifectiveness of the method of the present invention in controllingthe erosion of soil can be demonstrated by greenhouse experiments usingseeded soil.

In typical experiments, one square foot flats filled with untreatedhighly organic soil were seeded with a mixture of 65% Kentuckybluegrass, 30% redtop and 5% white clover. The flats were elevated to a33% slope from the horizontal and the liquid compositions sprayed onduplicate flats at a rate of 1,000 gallons per acre. The flats weremaintained at a temperature between 72 and F. After 24 hours, the flatswere subjected to spraying with an amount of water equal to a %-inchrainfall in 8 minutes and the flats observed for erosion. The flats werethen watered in the elevated position as required. After 8 days, thegermination of the seeds was observed and compared with the germinationof untreated flats. The results of these experiments are presented inthe table below, wherein erosion is rated on a scale of O to 3, asfollows:

O=no erosion l=slight erosionno to soil loss evident 2=erosionobservedloss of top soil evident 3=serious erosionlarge loss of top soilTABLE I Mixture of Emulsions Dilution 1 Erosion Product of Example 4 0Do 0 Volume of mixture to volumes of water.

Thus, it can be seen from Table I that the application of the liquidcomposition according to the method of the present invention preventedthe serious erosion which normally occurs under the conditions of thetest, as evidenced by the untreated control flats. It was further notedthat the germination of the seeds in the treated flats was equal to orgreater than the germination of seeds in the untreated flats. Theexperimental conditions used herein were severe enough to cause seriouserosion in untreated flats, but mild enough to test germinationindependent of the erosion of the top soil.

Experiments were also carried out to illustrate the effectiveness ofpesticidal chemical compounds when used in the soil stabilizingcompositions of this invention. For example, greenhouse flats ofunsterilized soil were seeded to a lawn mixture consisting of Kentuckybluegrass, reddimethylamine salt of 2-methoxy-3,6-dichlorobenzoic acidper acre. An untreated flat was maintained as a control.

At the end of 30 days, all the flats were inspected. The untreatedcontrol fiat had a count of 51 weeds per sq. ft., the weeds being pigweed, mustard, lambsquarters, and fox tail. The flat treated with theherbicidal chemical compound plus soil stabilizer emulsion, however, hada weed count of only 9 weeds per sq. ft., indicating an 82% decrease inweed population. The few remaining weeds were sickly in appearance. Thegrowth of the grasses in both the treated and untreated flats was normaland healthy.

We claim:

1. A method for the treatment of soil to reduce soil erosion whichcomprises applying to the soil surface a soil stabilizing amount of anaqueous composition comprising a mixture of (1) from about 20% to about85%, by weight of the mixture of a thermoplastic petroleum-derivedhydrocarbon resin-in-water emulsion, said resin having a softening pointof from about 50 to about 200 F., a mixed aniline point of from about 20to about 80 C., and an iodine number of from about 70 to to about 300;and

(2) from about 15% to about 80%, by weight of the mixture, of a linearpolymer-in-water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of or,B-ethylenically unsaturated di carboxylic acids whereinthe alkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof.

2. A method for the treatment of soil to reduce soil erosion whichcomprises applying to the soil surface a soil stabilizing amount of anaqueous composition comprising a mixture of (1) from about 20% to about85%, by weight of the mixture, of a thermoplastic, petroleum-derived,hydrocarbon resin-in-water emulsion, said resin having a softening pointof from about 50 to about 200 F., a mixed aniline point of from about 20to about 80 C., an iodine number of from about 70 to about 300, asaponification number of from to about 2 a flash point (Cleveland OpenCup) above 350 F., an A.P.I. gravity at 60 F. of from 0 to about 20degrees, a Gardner color (50% toluene) of from 1 to about 12, and amolecular weight of from about 300 to about 1400 as measured bycryoscopic means; and

(2) from about to about 80%, by weight of the mixture, of a linearpolymer-in-water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, viny acetate, acryates and methacrylates, copolymers of two ormore of said monomers, copolymers of said monomers with vinyl esters oflong chain fatty acids, copolymers of said monomers with di(alkylesters) of a,,8-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof.

3. A method for the treatment of soil to reduce soil erosion whichcomprises applying to the soil surface a soil stabilizing amount of anaqueous composition comprising from about 5% to about 20% by volume of amixture of (1) from about 20% to about 85%, by weight of the mixture, ofa thermoplastic, petroleum-derived h'ydrocarbon resin-in-Water emulsion,said resin having a softening point from about 50 to about 200 F., amixed aniline point of from about 20 to about C., an iodine number offrom about 70 to about 300, a saponification number of from 0 to about2, a flash point (Cleveland Open Cup) above 350 R, an A.P.I. gravity at60 F. of from 0 to about 20 degrees, a Gardner color (50% toluene) offrom 1 to about 12, and a molecular weight of from 300 to about 1400 asmeasured by cyroscopic means; and

(2) from about 15% to about 80%, by weight of the mixture of a linearpolymer-in-water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of a,B-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof.

4. A method for the treatment of soil to reduce soil erosion whichcomprises applying to the soil surface a soil stabilizing amount of anaqueous composition comprising from about 5% to about 20% by volume of amixture of (1) from about 20% to about by weight of the mixture of athermoplastic, petroluem-derived hydrocarbon resin-in-water emulsion,said resin having a softening point of from about 50 to about 200 F., amixed aniline point of from about 20 to about 80 C., an iodine number offrom about 70 to about 300, a saponification number of from 0 to about2, a flash point (Cleveland Open Cup) above 350 R, an A.P.I. gravity at60 F. of from 0 to about 20 degrees, a Gardner color (50% toluene) offrom 1 to about 12, and a molecular weight of from 300 to about 1400 asmeasured by cryoscopic means; and

(2) from about 15% to about 80%, by weight of the mixture, of a vinylacetate-di'butyl maleate copolymer polymer-in-water emulsion.

5. A method for the treatment of soil to reduce soil erosion whichcomprises applying to the soil surface a soil stabilizing amount of anaqueous composition comprising from about 5% to about 20% by volume of amixture of (1) from about 20% to about 85%, by weight of the mixture, ofa thermoplastic petroleum-derived, hydrocarbon resin-in-water emulsion,said resin composed substantially of tetramers and higher polymers ofconjugated aliphatic and cyclic dienes and having a softening point offrom about 50 to about F., a mixed aniline point of from about 40 toabout 80 C., an iodine number of from about 20 to about 300, asaponification number of from about 0 to about 2, a flash point(Cleveland Open Cup) above 350 R, an A.P.I gravity at 60 F. of from 0 toabout 20 degrees, a Gardner color 50% toluene) of from 1 to about 12,and a molecular weight of from 300 to about 600 as measured by cryosopicmeans; and

(2) from about 15% to about 80%, by weight of the mixture, of a vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion.

6. A method for the treatment of soil to reduce soil 75 erosion whichcomprises applying to the soil surface a 3,319,377 is 14 a soilstabilizing amount of an aqueous composition comdegrees, a Gardnercolor, (50% toluene) of from prising from about to about 20% by a volumeof a 1 to about 12, and a molecular we1ght of from about mixture of 300to about 1400 as measured by cryoscopic means;

(1) from about 20% to about 85%, by weight of the to about 20% by volumeof a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived, hydrocarbon resin-inwvater emulsion, said resin having a softening point of from about 50to about 200 F.,

and

mixture, of a thermoplastic petroleum-derived, sub- 5 (2) from about 15%to about 80%, by weight of the stantially completed polymerized,aromatic, hydromixture, of avinyl acetate-dibutylmaleatecopolymer carbonresin-in-water emulsion, said resin having a polymer-in-water emulsion.softening point of from about 100 to about 200 10. An aqueouscomposition comprislng from about F., a mixed aniline point of from 20to about 60 5% to about 20% by volume of a mixture of C., an iodinenumber of from about 70 to about (1) from about 20% to about 85%, byweight of the 220, a saponification number of fro-m O to about 2,mixture, or" a thermoplastic petroleum-derived, hydroa flash point(Cleveland Open Cup) above 425 F., carbon resin-in-water emulsion, saidresin composed an A.P.I. gravity at 60 F. of from O to about 10substantially of tetramers and higher polymers of degrees, a Gardnercolor (50% toluene) of from conjugated aliphatic and cyclic dienes andhaving a about 1 to about 12, and a molecular weight of from softeningpoint of from about 50 to about 100 F., 600 to about 1400 as measured bycryoscopic means; a mixed aniline point of from about 40 to about and 80C., an iodine number of from about 200 to about 2 from about 15% toabout 80%, by weight of the a sapbnifibatibn number of from 0 o aboutmixture, of vinyl acetate-dibutyl maleate copolymer a flash Point(Cleveland p p) above F"! ,polymer-in-water ul i an A.P.I. gravity at 60F. of from 0 to about 20 7. An aqueous composition comprising a mixtureof degrees, a Gardner Color t u of from 1 (1) from about 20% to bo t 85%by i ht f th to about 12, and a molecular weight of from 300 to mixtureof a thermoplastic petroleum-derived, hydroabout 600 as measured yofyoscouib means; carbon resin-in-water emulsion, said resin having afrom about 15% to about y Weight of the softening point of from about 50to about 200 F., 2:) mtXtuTo, of a Viny1 a y maleate p y a mixed anilinepoint of from about 20 to about p y omulslon. 80 C., and an iodinenumber of from about 70 to AH aquoous Composition comprising from aboutabout 300; and 5% to about 20% by volume of a mixture of 2 from about15% to about 80%, by weight of the from about to about y Weight f themixture, of a linear polymer-in-water emulsion, said mixtur of atbol'moplastio Petroleum-deified, polymer selected from the groupconsisting of homostal'ltlany completely polymerized, aromatic, ypolymers of vinyl alcohol, vinyl acetal, vinyl chloride, oarboufosiu-in-watol' emulsion, Said rosin having a vinyl acetate, acrylatesand methacrylates, copolymers sottonlug P u of tljom about to about oftwo or more of said monomers, copolymers of a muted auibue Polut from 20to about w said monomers with vinyl esters of long chain fatty iodiuonumber of from about 70 to about acids, copolymers of said monomers withdi(alkyl sapouffioatlou number of from 0 to about a esters) ofa,fi-ethylenically unsaturated dicarboxylic flash Polut (Cleveland p p)above -a acids wherein the alkyl ester group contains from 4 an gfayltyat Of from 0 to a ut 10 to l8carbon atoms, and mixtures thereof.degrees, a Gardner Color toluene) of from 8, A aqueous CompositionComprising about 5% 40 about 1 to about 12, and a molecular weight offrom to about 20% by volume of a mixture of 600 to about 1400 asmeasured by cryoscopic means;

(1) from about 20% to about 85%, by weight of the and mixture, of athermoplastic petroleum-derived, hydrofrom about 15% to about 80%, yWeight of the carbon resin-in-water emulsion, said resin having amixture, of Vinyl aootatodtbutyl maleate p y softening point of fromabout 50 to about 200 F., polymor-inl-watof emulsion. a i d ili point off about 20 to about 12. A method for the treatment of soil to reducesoil 80 C., an iodine number of from about 70 to about erosion and toControl Posts which comprises Pp y to 300, a saponification number of fo 0 to about 2 the soil surface a soil stabilizing amount of an aqueousa flash point (Cleveland Open Cup) above 350 F., Composition comprisinga miXturo of an A.P.I. gravity at 60 F. of from 0 to about 20 from about20% to about y Weight of the d a G d color (50% l f from mixture of athermoplastic petroleum-derived hydro- 1 to about 12, and a molecularWeight f f o 300 carbon resin-in-water emulsion, said resin having a toabout 1400 as measured by cryoscopic means; and Softening Point of fromabout to about (2) f b t 15% to about 30% b i h f h a mixed anilinepoint of from about 20 to about 80 mixture of a linear polymer-in-wateremulsion, said C, and an iodine number of from about 70 to about polymerselected from the group consisting of homopolymers of vinyl alcohol,vinyl acetal, vinyl chloride, from about 15% to about y Weight of thevinyl acetate, acrylates and methacrylates, copolymers mi ture, Of alinear polymer-in-water emulsion, said of two or more of aid monomercopolymers f polymer selected from the group consisting of homosaidmonomers with vinyl esters of long chain fatty polymers of vinylalcohol, vinyl acetal, vinyl chloride, acids, copolymers of saidmonomers with di(alkyl vinyl acetate, acrylates and methacrylates,copolyesters of ot,[3-ethyleneically unsaturated dicarboxylic mers oftwo or more of said monomers, copolymers acids wherein the alkyl estergroup contains from 4 0f aid m n mers With vinyl esters of long chain to18 carbon atoms, and mixtures thereof. fatty acids, copolymers of saidmonomers with di- 9. An aqueous composition comprising from about 5%(alkyl esters) of a,,8-ethylenically unsaturated dicarboxylic acidswherein the alkyl ester group contains from 4to 18 carbon atoms, andmixtures thereof; and (3) a pesticidal chemical compound. 13. A methodfor the treatment of soil to reduce soil erosion and to control pestswhich comprises applying to the soil surface a soil stabilizing amountof an aqueous composition comprising a mixture of a mixed aniline .pointof from about 20 to about C., an iodine number of from about 70 to about300, a saponification number of from 0 to about 2, a flash point(Cleveland Open Cup) above 350 R, an A.P.I. gravity at 60 F. of from 0to about 20 (1) from about 20% to about by weight of the mixture, of athermoplastic, petroleum-derived, hydrocarbon resin-in-water emulsion,said resin having a softening point of from about 50 to about 200 F., amixed aniline point of from about 20 to about 80 C., an iodine number offrom about 70 to about 300, a saponification number of from to about 2,a flash point (Cleveland Open Cup) above 350 F., an A.P.I. gravity of 60F. of from 0 to about 20 degrees, a Gardner color (50% toluene) of from1 to about 12, and a molecular weight of from about 300 to about 1400 asmeasured by cryoscopic means;

(2) from about 15% to about 80%, by weight of the mixture, of a linearpolymer-in-Water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of ufi-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof; and

(3) a pesticidally toxic amount of a pesticidal chemical compoundselected from the group consisting of herbicides, insecticides, andfungicides.

14. A method for the treatment of soil to reduce soil erosion and tocontrol weeds which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about 20% by volume of a mixture of (1) from about 20% to about85%, by weight of the mixture, of a thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-Water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about 70 to about 220, a saponificationnumber of from 0 to about 2, a flash point (Cleveland Open Cup) above425 R, an A.P.I, gravity at 60 F. of from 0 to about degrees, a Gardnercolor (50% toluene) of from about 1 to about 12, and a molecular weightof from 600 to about 1400 as measured by cryoscopic means; and (2) fromabout to about 80%, by Weight of the mixture, of vinyl acetate-dibutylmaleate copolymer polymer-in-water emulsion; and (B) of herbicidallytoxic amount of a herbicidal chemical compound.

15. A method for the treatment of soil to reduce soil erosion and tocontrol insects which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about by volume of a mixture of (1) from about 20% to about 85%,by weight of the mixture, of a thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-Water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about 70 to about 220, a saponificationnumber of from 0 to about 2, a flash point (Cleveland Open Cup) above425 R, an A.P.I. gravity at 60 F. of from 0 to about 10 degrees, aGardner color toluene) of from about 1 to about 12, and a molecularweight of from 600 to about 1400 as measured by cryoscopic means; and(2) from about 15% to about 80%, by weight of the mixture, of vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion; and (B) aninsecticidally toxic amount of an insecticidal chemical compound.

16. A method for the treatment of soil to reduce soil erosion and tocontrol fungi which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about 20% by volume of a mixture of (1) from about 20% to about85%, by weight of the mixture, of a thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about to about 220, a saponification numberof from 0 to about 2, a flash point (Cleveland Open Cup) above 425 F.,an A.P.I. gravity at 60 F. of from 0 to about 10 degrees, a Gardnercolor 50% toluene) of from about 1 to about 12, and a molecular Weightof from 600 to about 1400 as measured by cryoscopic means; and

(2) from about 15%to about by weight of the mixture, of vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion;

and (B) a fungicidally toxic amount of a fungicidal chemical compound.

17. An aqueous composition comprising a mixture of (1) from about 20% toabout by Weight of the mixture of a thermoplastic petroleum-derivedhydrocarbon resin-in-water emulsion, said resin having a softening pointof from about 50 to about 200 F., a mixed aniline point of from about 20to about 80 C., and an iodine number of from about 70 to about 300;

(2) from about 15% to about 80%, by Weight of the mixture, of a linearpolymer-in-water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of a,,8-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof; and

(3) a pesticidal chemical compound.

18. An aqueous composition comprising (A) from about 5% to about 20% byvolume of a mixture of (i) from about 20% to about 85%, by Weight of themixture, of a thermoplastic petroleum-derived hydrocarbon resin-in-wateremulsion, said resin having a softening point of from about 50 to about200 F., a mixed aniline point of from about 20 to about 80 C., an iodinenumber of from about 70 to about 300, a saponification number of from 0to about 2, a flash point (Cleveland Open Cup) above 350 R, an A.P.I.gravity at 60 F. of from 0 to about 20 degrees, a Gardner color (50%toluene) of from 1 to about 12, and a molecular Weight of from about 300to about 1400 as measured by cryoscopic means; and

(2) from about 15% to about 80%, by Weight of the mixture, of a vinylacetate-dibutyl maleate copolymer polymer-in-Water emulsion;

and (B) a pesticidally toxic amount of a pesticidal chemical compoundselected from the group consisting of herbicides, insecticides, andfungicides.

19. An aqueous composition comprising (A) from about 5% to about 20% byvolume of a mixture of (1) from about 20% to about 85%, by Weight of themixture, of a thermoplastic petroleum-derived, substantially completelypolymerized, aromatic, hydrocarbon resin-in-Water emulsion, said resinhaving a softening point of from about to about 200 F., a mixed anilinepoint of from 20 to about 60 C., an iodine number of from about 70 toabout 220, a saponification number of from 0 to about 2, a flash point(Cleveland Open Cup) above 425 R, an A.P.I. gravity at 60 F. of from 0to about 10 degrees, a Gardner color (50% toluene) of from about 1 toabout 12, and a molecular Weight of from 600 to about 1400 as measuredby cryoscopic means; and

a softening point of from about 50 to about 200 F., a mixed anilinepoint of from about 20 to about 80 C., an iodine number of from about 70to about 300, a saponification number of from to about 2, a flash point(Cleveland Open Cup) above 350 F., an A.P.I. gravity of 60 F. of from 0to about 20 degrees, a Gardner color (50% toluene) of from 1 to about12, and a molecular weight of from about 300 to about 1400 as measuredby cryoscopic means;

(2) from about 15% to about 80%, by weight of the mixture, of a linearpolymer-in-water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of a,fl-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof; and

(3) a pesticidally toxic amount of a pesticidal chemical compoundselected from the group consisting of herbicides, insecticides, andfungicides.

14. A method for the treatment of soil to reduce soil erosion and tocontrol weeds which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about 20% by volume of a mixture of (1) from about 20% to about 85by weight of the mixture, of a thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about 70 to about 220, a saponificationnumber of from 0 to about 2, a flash point (Cleveland Open Cup) above425 F., an A.P.I. gravity at 60 F. of from 0 to about degrees, a Gardnercolor (50% toluene) of from about 1 to about 12, and a molecular weightof from 600 to about 1400 as measured by cryoscopic means; and

(2) from about to about 80%, by weight of the mixture, of vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion;

and (B) of herbicidally toxic amount of a herbicidal chemical compound.

15. A method for the treatment of soil to reduce soil erosion and tocontrol insects which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about by volume of a mixture of (1) from about 20% to about 85 byweight of the mixture, of a'thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about 70 to about 220, a saponificationnumber of from 0 to about 2, a flash point (Cleveland Open Cup) above425 R, an A.P.I. gravity at 60 F. of from 0 to about 10 degrees, aGardner color (50% toluene) of from about 1 to about 12, and a molecularweight of from 600 to about 1400 as measured by cryoscopic means; and

(2) from about 15% to about 80%, by weight of the mixture, of vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion;

and (B) an insecticidally toxic amount of an insecticidal chemicalcompound.

16. A method for the treatment of soil to reduce soil erosion and tocontrol fungi which comprises applying to the soil surface a soilstabilizing amount of an aqueous composition comprising (A) from about5% to about 20% by volume of a mixture of (1) from about 20% to about85%, by weight of the mixture, of a thermoplastic petroleum-derived,substantially completely polymerized, aromatic, hydrocarbonresin-in-water emulsion, said resin having a softening point of fromabout 100 to about 200 F., a mixed aniline point of from 20 to about 60C., an iodine number of from about 70 to about 220, a saponificationnumber of from 0 to about 2, a flash point (Cleveland Open Cup) above425 R, an A.P.I. gravity at 60 F. of from 0 to about 10 degrees, aGardner color 50% toluene) of from about 1 to about 12, and a molecularweight of from 600 to about 1400 as measured by cryoscopic means; and

(2) from about 15%to about by weight of the mixture, of vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion;

and (B) a fungicidally toxic amount of a fungicidal chemical compound.

17. An aqueous composition comprising a mixture of (1) from about 20% toabout by weight of the mixture of a thermoplastic petroleum-derivedhydrocarbon resin-in-water emulsion, said resin having a softening pointof from about 50 to about 200 F., a mixed aniline point of from about 20to about 80 C., and an iodine number of from about 70 to about 300;

(2) from about 15% to about 80%, by weight of the mixture, of a linearpolymer-in-Water emulsion, said polymer selected from the groupconsisting of homopolymers of vinyl alcohol, vinyl acetal, vinylchloride, vinyl acetate, acrylates and methacrylates, copolymers of twoor more of said monomers, copolymers of said monomers with vinyl estersof long chain fatty acids, copolymers of said monomers with di(alkylesters) of a,/3-ethylenically unsaturated dicarboxylic acids wherein thealkyl ester group contains from 4 to 18 carbon atoms, and mixturesthereof; and

( 3) a pesticidal chemical compound.

18. An aqueous composition comprising (A) from about 5% to about 20% byvolume of a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived hydrocarbon resin-in-wateremulsion, said resin having a softening point of from about 50 to about200 F., a mixed aniline point of from about 20 to about 80 C., an iodinenumber of from about 70 to about 300, a saponification number of from 0to about 2, a flash point (Cleveland Open Cup) above 350 R, an A.P.I.gravity at 60 F. of from 0 to about 20 degrees, a Gardner color (50%toluene) of from 1 to about 12, and a molecular Weight of from about 300to about 1400 as measured by cryoscopic means; and

(2) from about 15% to about 80%, by weight of the mixture, of a vinylacetate-dibutyl maleate copolymer polymer-in-water emulsion;

and (B) a pesticidally toxic amount of a pesticidal chemical compoundselected from the group consisting of herbicides, insecticides, andfungicides.

19. An aqueous composition comprising (A) from about 5% to about 20% byvolume of a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived, substantially completelypolymerized, aromatic, hydrocarbon resin-in-water emulsion, said resinhaving a softening point of from about to about 200 F., a mixed anilinepoint of from 20 to about 60 C., an iodine number of from about 70 toabout 220, a saponification number of from 0 to about 2, a flash point(Cleveland Open Cup) above 425 F an A.P.I. gravity at 60 F. of from 0 toabout 10 degrees, a Gardner color (50% toluene) of from about 1 to about12, and a molecular weight of from 600 to about 1400 as measured bycryoscopic means; and

8,319,377 is re soil stabilizing amount of an aqueous compositioncomdegrees, 21 Gardner color, (50% toluene) of from prising from aboutto about 20% by a volume of a 1 to about 12, and a molecular weight offrom about mixture of 300 to about 1400 as measured by cryoscopic means;

(1) from about 20% to about 85%, by weight of the and mixture, of athermoplastic petroleurn-derived, sub- (2) from about 15% to about 80%,by weight of the stantially completed polymerized, aromatic,hydromixture, of a vinyl acetate-dibutyl rnaleate copolymer carbonrcsin-in-water emulsion, said resin having a polymer-in-water emulsion.softening point of from about 100 to about 200 10. An aqueouscomposition comprising from about F., a mixed aniline point of from 20to about 60 5% to about 20% by volume of armxture of C., an iodinenumber of from about 70 to about (1) from about 20% to about 85%, byweight of the 220, a saponification number of from 0 to about 2, a flashpoint (Cleveland Open Cup) above 425 R, an A.P.I. gravity at 60 F. offrom 0 to about 10 degrees, a Gardner color (50% toluene) of frommixture, of a thermoplastic petroleum-derived, hydrocarbonresin-in-water emulsion, said resin composed substantially of tetramersand higher polymers of conjugated aliphatic and cyclic dienes and havinga about 1 to about 12, and a molecular weight of from softening point offrom about 50 to about 100 F., 600 to about 1400 as measured bycryoscopic means; a mixed aniline point of from about 40 to about and 80C., an iodine number of from about 200 to about (2) from about 15% tabout 80%, by Weight f th 300, a saponifieation number of from 0 toabout 2, mixture, of vinyl acetate-dibutyl maleate copolymer a flash poi(Cleveland p up) above 350 F., .polym r-in-wate emulsion, an A.P.l.gravity at 60 F. of from 0 to about 20 7. An aqueous compositioncomprising a mixture of degrees, a Gardner Color t of from 1 (1) fromabout 20% to about 85% by weight of the to about and a molecular Weightof from 300 to mixture of a thermoplastic petroleum-derived, hydroabout600 as measured y y p o carbon resin-in-water emulsion, said resinhaving a from about 15% to t y weight of the softening point of fromabout 50 to about 200 F., mixture, of a Vibyl aootuto-dlbutyl maloatooopolymof a mixed aniline :point of from about 20 to aboutpolymer-in-water emulsion.

80 C., and an iodine number of from about 70 to about 300; and (2) fromabout 15% to about 80%, by weight of the 11. An aqueous compositioncomprising from about 5% to about 20% by volume of a mixture of (1) fromabout 20% to about 85 by weight of the mixture, of a linearpolymer-in-Water emulsion, said u a thermoplastic po t polymer selectedfrom the group consisting of homo- Manually omp y p y e a y polymers ofvinyl alcohol, vinyl acetal, vinyl chloride, Carbou uemulslon, SoldToslu having a vinyl acetate, acrylates and methacrylates, copolymerssoftoulug po u of fljoln about to about f two or more f Said monomerscopolymers f a mixed amlme point of from 20 to about 60 C., saidmonomers with vinyl esters of long chain fatty on iodtuo number of fromabout 70 to about acids, copolymers of said monomers with di(alky1 a sapnl nu'mbor of from 0 to about esters) of a,fi-ethylenically unsaturateddicarboxylic flash Polnt (Cleveland p p) above acids wherein the alkylester group contains from 4 an gravlty at Of m 0 I about 1 to 18 carbonatoms, and mixtures thereof. dogfoos, a Gardner Color toluene) of from8, A aqueous compgsition Comprising f about 5% 40 about 1 to about 12,and a molecular weight of from to about 20% by ol of a mixture of 600 toabout 1400 as measured by cryoscopic means;

(1) from about 20% to about 85 by weight of the and mixture, of athermoplastic petroleum-derived, hydrofrom about 15% to about 30%, yWeight of the carbon resin-in-Water emulsion, said resin having amixturo, o Vinyl '3ootato"dib11ty1 maloato oopolymor softening point offrom about 50 to about 200 F., Polymorumwator Emulsiona mixed anilinepoint of from about 20 to about 80 C., an iodine number of from about 70to about 300, a saponification number of from 0 to about 2, a flashpoint (Cleveland Open Cup) above 350 F, an A.P.I. gravity at 60 F. offrom 0 to about 20 5O 12. A method for the treatment of soil to reducesoil erosion and to control pests which comprises applying to the soilsurface a soil stabilizing amount of an aqueous composition comprising amixture of (1) from about 20% to about 85%, by weight of the degrees, aGardner color toluene) of from 1 to about 12, and a molecular weight offrom 300 to about 1400 as measured by cryoscopic means; and (2) fromabout 15% to about 80%, by weight of the mixture of a thermoplasticpetroleum-derived hydrocarbon resin-in-water emulsion, said resin havinga softening point of from about 50 to about 200 F., a mixed anilinepoint of from about 20 to about 80 mixture of a linear polymer-in-wateremulsion, said and an iodine number f r m a ut 70 to about polymerselected from the group consisting of homopolymers of vinyl alcohol,vinyl acetal, vinyl chloride, from vabout 15% to about y Weight of thovinyl acetate, acrylates and methacrylates, copolymers mi r f a linear py remulsion, Said of two or more of said monomers, cop-olymers ofpolymer selected from the group consisting of homosaid monomers withvinyl esters of long chain fatty polymers of vinyl alcohol, vinylacetal, vinyl chloride,

acids, copolymers of said monomers with di(alkyl esters ofe,B-ethyleneically unsaturated dicarboxylic acids wherein the alkylester group contains from 4 to 18 carbon atoms, and mixtures thereof.

vinyl acetate, acrylates and methacrylates, copolymers of two or more ofsaid monomers, copolymers of said monomers with vinyl esters of longchain fatty acids, copolymers of said monomers with di- (alkyl esters)of a,,8-ethylenically unsaturated dicarboxylic acids wherein the alkylester group contains from 4 to 18 carbon atoms, and mixtures thereof;and

9. An aqueous composition comprising from about 5% to about 20% byvolume of a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived, hydro- (3) a pesticidalchemical compound. carbon resin -in-water emulsion, said resin having a13. A method for the treatment of soil to reduce soil softening point offrom about 50 to about 200 F., erosion and to control pests whichcomprises applying to a mixed aniline point of from about 20 to aboutthe soil surface a soil stabilizing amount of an aqueous C., an iodinenumber of from about 70 to about composition comprising a mixture of300, a saponification number of from 0 to about 2, (1) from about 20% toabout by weight of the a flash point (Cleveland Open Cup) above 350 F,mixture, of a thermoplastic, petroleum-derived, hyan A.P.I. gravity at60 F. of from 0 to about 20 75 drocarbon resin-in-water emulsion, saidresin having 17 (2) from about 15 to about 80%, by weight of themixture, of vinyl acetate-dibutyl maleate copolymer polymer-in-wateremulsion; and (B) a herbicidally toxic amount of a herbicidal chemicalcompound.

20. An aqueous composition comprising (A) from about to about 20% ofvolume of a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived, substantially completelypolymerized, aromatic, hydrocarbon resin-in-water emulsion, said resinhaving a softening point of from about 100 to about 200 F., a mixedaniline point of from 20 to about 60 C., an iodine number of from about70 to about 220, a saponification number of from 0 to about2, a fiashpoint (Cleveland Open Cup) above 425 R, an A.P.I. gravity at 60 F. offrom 0 to about degrees, a Gardner color (50% toluene) of from about 1to about 12, and a molecular weight of from 600 to about 1400 asmeasured by cryoscopic means; and (2) from about to about 80%, by weightof the mixture, of vinyl acetate-dibutyl maleate copolymerpolymer-in-water emulsion; and (B) an insecticidally toxic amount of aninsecticidal chemical compound.

21. An aqueous composition comprising (A) from about 5% to about byvolume of a mixture of (1) from about 20% to about 85%, by weight of themixture, of a thermoplastic petroleum-derived, substantially completelypolymerized, aromatic, hydrocarbon resin-in-water emulsion, said resinhaving a softening point of from about 100 to about 200 R, a mixedaniline point of from 20 to about C., an iodine number of from about toabout 220, a saponification number of from O to about 2, a flash point(Cleveland Open Cup) above 425 R, an AP. gravity at 60 F. of from 0 toabout 10 degrees, a Gardner color (50% toluene) of from about 1 to about12, and a molecular Weight of from 600 to about 1400 as measured bycryoscopic means; and (2) from about 15% to about by weight of themixture, of vinyl acetate-dibutyl maleate copolymer polymer-in-wateremulsion;

and (B) a fungicidally toxic amount of a fungicidal chemical compound.

References Cited by the Examiner UNITED STATES PATENTS 2,798,867 7/1957Gordon et a1. 260-805 2,961,799 11/1960 Coe 47-9 3,077,054 2/ 1963Niemeijer 26029.6

25 MURRAY TILLMAN, Primary Examiner.

J. L. WHITE, Assistant Examiner.

1. A METHOD FOR THE TREATMENT OF SOIL TO REDUCE SOIL EROSION WHICHCOMPRISES APPLYING TO THE SOIL SURFACE A SOIL STABILIZING AMOUNT OF ANAQUEOUS COMPOSITION COMPRISING A MIXTURE OF (1) FROM ABOUT 20% TO ABOUT85%, BY WEIGHT OF THE MIXTURE OF A THERMOPLASTIC PETROLEUM-DERIVEDHYDROCARBON RESIN-IN-WATER EMULSION, SAID RESIN HAVING A SOFTENING POINTOF FROM ABOUT 50* TO ABOUT 200*F., A MIXED ANILINE POINT OF FROM ABOUT20* TO ABOUT 80*C, AND AN IODINE NUMBER OF FROM ABOUT 70 TO TO ABOUT300; AND (2) FROM ABOUT 15% TO ABOUT 80%, BY WEIGHT OF THE MIXTURE, OF ALINEAR POLYMER-IN-WATER EMULSION, SAID POLYMER SELECTED FROM THE GROUPCONSISTING OF HOMOPOLYMERS OF VINLY ALCOHOL, VINYL ACETAL, VINYLCHLORIDE, VINYL ACETATE, ACRYLATES AND METHACRYLATES, COPOLYMERS OF TWOOR MORE OF SAID MONOMERS, COPOLYMERS OF SAID MONOMERS WITH VINYL ESTERSOF LONG CHAIN FATTY ACIDS, COPOLYMERS OF SAID MONOMERS WITH DI(ALKYLESTERS) OF A,B-ETHYLENICALLY UNSATURATED DICARBOXYLIC ACIDS WHEREIN THEALKYL ESTER GROUP CONTAINS FROM 4 TO 18 CARBON ATOMS, AND MIXTURESTHEREOF.